CN104588121B - Hydrocracking catalyst carrier and preparation method thereof - Google Patents

Abstract

The invention discloses a hydrocracking catalyst carrier and a preparation method thereof. The catalyst carrier is composed of a small-grain Y type molecular sieve, amorphous silica-alumina and alumina. According to the preparation method, the small-grain Y type molecular sieve with the characteristics of proper dealumination degree, good crystallinity retentivity and well-developed secondary pores is used as an acid component; and when the small-grain Y type molecular sieve and the amorphous silica-alumina are cooperatively used for preparing a hydrocracking catalyst, the hydrocracking catalyst has the advantages of good activity, heavy naphtha selectivity and superior product quality.

Description

Carrier of hydrocracking catalyst and preparation method thereof

Technical field

The present invention relates to a kind of carrier of hydrocracking catalyst and preparation method thereof, more specifically a kind of to contain little crystal grain Carrier of hydrocracking catalyst of Y type molecular sieve and preparation method thereof.

Background technology

Hydrocracking technology is one of crude oil secondary operation, the important means of heavy oil lighting, because it is fitted to raw material Ying Xingqiang, operation and products scheme are all very flexibly and the features such as good product quality, it has also become production high grade light-end products and Solve the important channel in industrial chemicals source.

The key of hydrocracking technology is catalyst.It is required that catalyst newly developed has higher active, selectivity, with Device is improved to the adaptability of raw material and the flexibility of processing scheme, voluminous high benefit component, reducing energy consumption, increases benefit.

Carrier is the important component part of catalyst, not only dispersion place is provided for metal active constituent, while carrier sheet Body also assists in reaction, cooperates with together with other active components and completes whole catalytic reaction, and hydrocracking catalyst is a kind of pair of work( Energy catalyst, it is simultaneously containing acidic components and hydrogenation component.Hydrogenation activity is selected generally from VI B races in the periodic table of elements and VIII race's metal is provided；And its acidic components is mainly provided by zeolite and inorganic oxide, major part is with aluminum oxide or without fixed Shape sial is carrier, is equipped with a certain amount of molecular sieve.And the key component that cracking is played in such catalyst is usually Y molecules Sieve, the quality of Y molecular sieve performance directly affects the performance and product quality of catalyst.

Y type molecular sieve is cracking active component that at present can be the most universal in residual oil cracking field, and crystal grain is generally 1000nm or so, its crystal grain is larger, and duct is relatively long, and diffusional resistance is big, and macromolecular is difficult to be reacted into inside duct, Product is also more difficult after reaction diffuses out, so the selectivity of its cracking activity and purpose product receives restriction.With conventional Y types Molecular sieve is compared, and small crystal grain Y-shaped molecular sieve has bigger external surface area and more outer surface activated centres, is conducive to improving big point Sub- hydrocarbon cracking capability, thus with more superior catalytic perfomance.Meanwhile, reducing Y type molecular sieve crystallite dimension can be with Improve inner surface active sites utilization rate.In general, diffusion of the reactant molecule in molecular sieve endoporus duct is referred to as transgranular expansion Dissipate.Molecular sieve inner surface is set all to be used for catalyzed conversion, it is necessary to make micropore diffusion speed be more than endoporus catalyzed conversion Speed.It is the best way to shorten diffusion path.The effective way that micropore diffusion is limited is overcome to be to reduce zeolite crystal Size.This can not only increase the external surface area of zeolite crystal, and while shorten diffusion length.EP0204236 is to little Crystal NaY molecular sieve and big crystal grain NaY molecular sieve are compared, and are as a result shown, the former has higher to RFCC Active and preferable selectivity.

Small crystal grain NaY molecular sieve is that do not possess acidity, and needs are modified process, to meet the performance of Cracking catalyst Require.CNl382632A discloses a kind of super stabilizing method of small-grain Y-type zeolite, and the method is to be dried gas with silicon tetrachloride Body and fine grain NaY zeolitic contact, obtain after washing, due to the heat and hydrothermal stability of its raw material itself it is just poor, while The inventive method is to process molecular sieve by the way of gas phase dealumination complement silicon, and this causes the heat and hydrothermal stability of product worse, Activity is low.Especially poor to heat endurance and hydrothermal stability fine grain NaY zeolite, the sial skeleton structure in molecular sieve Less stable, easily causes the removing of framework aluminum in modifying process, at the same also some framework silicon also with removing, Easily cause the phenomenon that caving in occurs in part skeleton so that the crystallization reservation degree of product is relatively low, and the activity of molecular sieve is not high.

CN200910188140.5 discloses a kind of hydrocracking catalyst and preparation method thereof.The catalyst includes hydrogenation The carrier of active metal component and small-grain Y molecular sieve, amorphous silica-alumina and aluminum oxide composition, wherein the small-grain Y-type point Son sieve be using hydro-thermal process after small crystal grain Y-shaped molecular sieve.Raw materials used small crystal grain NaY molecular sieve is in CN101722023A Prepared by disclosed method, i.e. SiO₂/Al₂O₃Mol ratio be 4.0～6.0, average grain diameter in 100～700nm, after passing sequentially through The mixed aqueous solution of continuous modified i.e. ammonium exchange, ammonium hexafluorosilicate dealumination complement silicon, hydro-thermal process, aluminium salt and acid is processed, and obtains little crystalline substance Grain Y molecular sieve.In the method, after needing that first raw material is processed with ammonium hexafluorosilicate dealumination complement silicon, then the process such as hydro-thermal process is carried out, The skeleton structure that molecular sieve could so be reduced is caved in, and improves the crystallization reservation degree of molecular sieve, but the method is due to first with six After the process of ammonium fluosilicate dealumination complement silicon, due to there are sial same order elements, molecular sieve silica constructed of aluminium is than more complete, then enters water-filling Heat treatment, the secondary pore of formation is few, and secondary pore proportion is low, and used as catalyst molecule screen banks point, purpose product selectivity is low.

In preparation process, silicon and aluminium are easy to run off existing method fine grain NaY type molecular sieve, and silicon utilization rate is low, and silicon, Reuniting, easily occurs in aluminium distributing inhomogeneity, therefore existing method still cannot prepare silica alumina ratio height, and heat endurance and hydro-thermal are steady Qualitative and good fine grain NaY type molecular sieve.Through successive modified, it is impossible to obtain structural integrity, degree of crystallinity is high and with more The small crystal grain Y-shaped molecular sieve of secondary pore, used as the cracking component of catalyst, purpose product yield is low.

The content of the invention

For weak point of the prior art, the invention provides a kind of good hydrocracking catalyst of catalytic performance is carried Body and preparation method thereof.The carrier of hydrocracking catalyst is adopted and provides a kind of higher silica alumina ratio, high-crystallinity, secondary pore Many, bigger serface small crystal grain Y-shaped molecular sieve has higher work as acidic components, prepared hydrocracking catalyst Property, heavy naphtha is selective and excellent product property.

Carrier of hydrocracking catalyst of the present invention, is made up of small crystal grain Y-shaped molecular sieve, amorphous silica-alumina and aluminum oxide, its Described in small crystal grain Y-shaped molecular sieve, its property is as follows：SiO₂/A1₂O₃Mol ratio 10 less than 40, preferably 15 ~ 38, average grain diameter be 200～700nm, preferably 300～500nm, relative crystallinity more than 100%, preferably 100% ~ 120%, 2.430～2.450nm of lattice constant, preferably 2.435～2.445nm, specific surface area is 850～1000m²/ g, pore volume For 0.50～0.80mL/g, the pore volume shared by the secondary pore of 1.7～10nm accounts for more than the 50% of total pore volume, and preferably 50% ~ 65%, Na₂O content≤0.15wt%.

Carrier of hydrocracking catalyst property of the present invention is as follows：Specific surface area is 450～650 m²/ g, pore volume is 0.5～ 0.80 mL/g, the pore volume of 4 ~ 10nm of aperture accounts for the 45%～80% of total pore volume, preferably 45%～60%.

Described carrier of hydrocracking catalyst, on the basis of the weight of carrier, its composition includes：Small-grain Y-type molecule The content of sieve is 15wt%～50wt%, preferably 20wt%～40wt%, and the content of amorphous silica-alumina is 20wt%～60wt%, excellent Elect 30wt%～50wt% as, the content of aluminum oxide is 10wt%～30wt%, preferably 15wt%～30wt%.

The preparation method of carrier of hydrocracking catalyst of the present invention, including：By small crystal grain Y-shaped molecular sieve, amorphous silica-alumina With adhesive mixing, extruded moulding, then drying and roasting, make carrier.

Described small-grain Y molecular sieve, including following preparation process：

（1）The preparation of fine grain NaY type molecular sieve；

（2）By fine grain NaY with containing alkaline solution treatment；

（3）By step（2）The fine grain NaY type molecular sieve for obtaining is prepared into Na₂The little crystal grain of O content≤2.5wt% NH₄NaY；

（4）To step（3）Obtain little crystal grain NH₄NaY molecular sieve carries out hydro-thermal process；

（5）By step（4）The molecular sieve for obtaining is with containing NH₄ ⁺And H⁺Mixed solution process, it is scrubbed and be dried, obtain Small crystal grain Y-shaped molecular sieve；

Step（1）Described in small crystal grain NaY molecular sieve, its property is as follows：SiO₂/Al₂O₃Mol ratio is more than 6.0 and not Higher than 9.0, preferably 6.5～9.0, more preferably 7.0～8.0, average grain diameter be 200～700nm, preferably 300～ 500nm；Specific surface area is 800～1000 m²/ g, preferably 850～950 m²/ g, 0.30/～0.45mL/g of pore volume, relative knot Brilliant degree is 90%～130%, and cell parameter is 2.460～2.470nm, the relative crystallinity Jing after roasting in 650 DEG C of air 3 hours It is relative Jing after 700 DEG C of water vapour hydro-thermal process 2 hours for more than 90%, generally 90%～110%, preferably 90% ~ 105% Degree of crystallinity is more than 90%, generally 90%～110%, preferably 90% ~ 105%.

In the inventive method in step (1) fine grain NaY type molecular sieve preparation method, including：

I, preparation directed agents：Silicon source, silicon source, alkali source and water are fed intake according to following proportioning：(6～30) Na₂O：Al₂O₃：(6 ～30) SiO₂：(100～460) H₂O, after stirring, stirs mixture ageing and is obtained for 0.5～24 hour at 0～20 DEG C Directed agents；

II, using preparing amorphous silicon alumnium using carbonization predecessor, the weight with the butt of amorphous silica-alumina predecessor is as base Standard, the content that silicon is counted with silica as 40wt%～75wt%, preferably 55 wt%～70wt%；Its preparation process includes：

A, respectively preparation sodium aluminate solution and sodium silicate solution；

The part sodium silicate solution for adding step a to prepare in b, the sodium aluminate solution prepared to step a, then passes to CO₂ Gas, controlling reaction temperature is 10 ~ 40 DEG C, and preferably 15～35 DEG C, the pH value for controlling cemented into bundles is 8 ~ 11；Wherein when being passed through CO₂Gas flow accounts for the 60% ~ 100% of total intake, when preferably 80% ~ 100%, adds remainder sodium silicate solution, wherein Remainder sodium silicate solution accounts for step b addition sodium silicate solution total amount in terms of silica in terms of silica in step b 5wt% ~ 85wt%, preferably 30wt% ~ 70wt%；

C, at the control temperature and pH value of step b, said mixture ventilation stablize 10 ~ 30 minutes；

III, prepare silica-alumina gel

By (0.5～6) Na₂O：Al₂O₃：(8～15) SiO₂：(100～460) H₂Total molar ratio of O, at 0～40 DEG C To step under conditions of quick stirring（2）Water, silicon source, directed agents and alkali source are added in the amorphous silica-alumina predecessor of gained, and Control ph is 9.5 ~ 12.0, and uniform stirring obtains silica-alumina gel；Wherein directed agents addition accounts for the 1% of silica-alumina gel weight ～20%,

The step dynamic crystallizations of reactant mixture Jing two obtained by IV, step III, then Jing filtrations, washing, are dried, and obtain little crystalline substance Grain NaY molecular sieve.

In the present invention, in step I and III, silicon source, alkali source are respectively selected from sodium metasilicate and NaOH.In step I, silicon source Selected from sodium metaaluminate.

In step II, the concentration of the sodium aluminate solution used by step a is preferably 15～55g Al₂O₃/ l, sodium silicate solution Concentration be 50～150 gSiO₂/ l, CO used by step b₂The concentration of gas is 30v% ~ 60v%.

In step III, 0～40 DEG C of controlling reaction temperature, preferably 10 ~ 30 DEG C, pH value 9.5～12.0, preferable ph 10～ 11。

In step IV, the reactant mixture of gained carries out crystallization using two step dynamic crystallizations, and the wherein first step enters Mobile state The condition of crystallization is as follows：At 50～90 DEG C, crystallization time is 0.5～18 hour to temperature control；Second step carries out dynamic crystallization Condition is as follows：At 80～140 DEG C, crystallization time is 3～10 hours to temperature control, and after the completion of crystallization, then Jing is filtered, washs, done It is dry, product is obtained.Two step dynamic crystallization conditions are preferably as follows：The first step：Temperature control at 60～80 DEG C, crystallization time is 1～ 10 hours；Second step：At 80～120 DEG C, crystallization time is 5～10 hours to temperature control.

Step（2）In, the aqueous solution beating of small crystal grain NaY molecular sieve and alkali is well mixed, and maintain 60～120 DEG C 1～4h of stir process under temperature conditionss, filters, washes.Alkali wherein used is the mixture of NaOH, KOH or NaOH and KOH. The concentration of the aqueous solution of alkali is generally 0.1～3 mol/L, and the concentration of molecular sieve is 0.05～1.0g/mL in slurries.

Step（4）In, the condition of described hydro-thermal process is as follows：Treatment temperature is controlled at 500～750 DEG C, preferred control At 600～700 DEG C, pressure is 0.01～0.50MPa, and preferably 0.05～0.30MPa, process time is 1.0～4.0 hours.

Step（5）In, by the molecular sieve after hydro-thermal process with acid and containing NH₄ ⁺Salt composition mixed solution contact, exchange Na in molecular sieve⁺With the part non-framework aluminum in removing molecular sieve, acid therein can be in hydrochloric acid, carbonic acid, nitric acid, sulfuric acid One or more, containing NH₄ ⁺Salt be containing above acid group ammonium salt in one or more；H in mixed solution⁺Concentration be 0.05～0.6mol/L, NH₄ ⁺Concentration be 0.5～3.0mol/L, exchange temperature be 70～120 DEG C, exchange slurries in molecular sieve Concentration be 0.1～0.5g/mL, swap time be 0.5～3.0 hour, exchange step may be repeated 1～4 time.Then remove Mother liquor, washes with water, is dried.

Other operating procedures in the modified Y molecular sieve preparation method of the present invention, such as ammonium salt are exchanged can be normal using this area The method of operating and condition of rule.Step（3）The method exchanged using ammonium salt, it is specific as follows：With NaY molecular sieve as raw material, using can The aqueous solution of undissolved ammonium salt is exchanged 0.5～3.0 hour at 70～120 DEG C at preferably 80～100 DEG C, and Y molecular sieve is exchanging slurry Concentration in liquid is 0.05～0.50g/mL, and repeated exchanged l～5 time filter off mother liquor, and washing is dried.Ammonium salt such as ammonium chloride, carbon One or more in sour ammonium, ammonium nitrate, ammonium sulfate, ammonium acetate, ammonium oxalate, ammonium citrate etc., the concentration of ammonium salt solution is 0.5 ～5.0mol/L.

Adhesive therefor of the present invention is made up of little porous aluminum oxide and inorganic acid and/or organic acid.Aperture oxidation used Aluminium pore volume is 0.3～0.5 mL/g, and specific surface area is 200～400m²/g。

In catalyst carrier of the present invention, amorphous silica-alumina used is mixed with small-grain Y molecular sieve and adhesive can be by altogether Prepared by the precipitation method or grafting copolymerization process, prepare by conventional method in document.SiO in obtained amorphous silica-alumina₂Weight Content is 20%～60%, preferably 25%～40%, and the pore volume of amorphous silica-alumina is 0.6～1.1 mL/g, preferably 0.8～ 1.0 mL/g, specific surface area is 300～500 m²/ g, preferably 350～500 m²/g。

Catalyst of the present invention can be molded according to actual needs, and shape can be cylindrical bars, clover etc..Catalyst into During type, shaping assistant, such as peptization acid, extrusion aid can also be added.Catalyst carrier of the present invention is using conventional method It is dried and roasting, it is specific as follows：It is dried 3～10 hours at a temperature of 80 DEG C～150 DEG C and in 500 DEG C～600 DEG C roastings Burn 3～6 hours.

When catalyst carrier of the present invention is used to prepare hydrocracking catalyst, load side conventional in prior art can be adopted Method, preferred infusion process can be saturation leaching, excessive leaching or be complexed leaching, i.e., be catalyzed with the solution impregnation containing required active component Agent carrier, the carrier after dipping is obtained final hydrocracking catalyst after drying, roasting.

Carrier of hydrocracking catalyst of the present invention due to using small crystal grain Y-shaped molecular sieve as acidic components, the molecular sieve The characteristics of with compared with high silica alumina ratio, high-crystallinity, many secondary pores, bigger serface, it is engaged with amorphous silica-alumina, especially fits Cooperate as light oil type hydrogen cracking catalyst carrier.

Due to the small-grain Y molecular sieve that catalyst carrier of the present invention is adopted, the silica alumina ratio of its NaY type Molecular sieve raw material compared with Height, degree of crystallinity is high, good stability, so in follow-up modification process, the crystal structure that saboteur does not sieve, and do not affect The stability of final molecular sieve.Molecular sieve of the present invention has carried out alkali process before ammonium exchange, is engaged with hydro-thermal process afterwards, Preferable dealumination depth is reached, and has preferably maintained molecular sieve structure, while generate by substantial amounts of secondary pore, not only Promote the performance of hydrogenation activity, and be conducive to the diffusion of product, hold charcoal ability and also greatly enhance, reduce and excessively split The occurrence probability of solution and second pyrolysis, has the selective and excellent product of activity, heavy naphtha well so as to make catalyst Moral character matter.

Adopt small crystal grain molecular sieve for Cracking Component in carrier of the present invention in addition, with bigger external surface area and it is more outward Active sites, are conducive to improving macromolecular hydrocarbon cracking capability, can make being hydrocracked for active component by this molecular sieve The activity increase of catalyst, while the performance of catalyst hydrogenation performance can be advantageously promoted.

Specific embodiment

In order to the present invention is better described, with reference to embodiment and comparative example the present invention is further illustrated.But this Bright scope is not limited solely to the scope of these embodiments.Analysis method of the present invention：Specific surface area, pore volume adopt low temperature liquid nitrogen physics Absorption method, relative crystallinity and cell parameter adopt x-ray diffraction method, silica alumina ratio to adopt chemical method, and the crystal grain of molecular sieve is big It is little to be determined by the way of SEM (SEM).Wt% is mass fraction.

Embodiment 1

The present embodiment is preparing raw material small crystal grain NaY molecular sieve

The preparation of NY-1

（1）The preparation of directed agents：Take 10 g sodium hydrate solids to be dissolved in 80g water, add sodium metaaluminate 2g (Al₂O₃Contain Measure as 45wt%, Na₂O content is 41wt%), then add 36g waterglass (SiO₂Content is 28wt%, Na₂O content is 8 Wt%), in 15 DEG C of stirring 4 hours prepared directed agents of ageing after being well mixed.

（2）The preparation of amorphous silica-alumina predecessor

Solid sodium aluminate is configured to into concentration for 40gAl₂O₃/ L sodium aluminate working solutions, take containing SiO₂The silicic acid of 28wt% Sodium solution, then concentration is diluted to for 100g SiO₂/ L sodium metasilicate working solutions.Take 1L sodium aluminate working solutions and be placed in plastic cans In, 0.2L sodium metasilicate working solutions are subsequently adding, 20 DEG C of controlling reaction temperature is passed through the CO that concentration is 50v%₂Gas, works as pH value Stop logical CO when reaching 10.0₂, 0.4L sodium metasilicate working solutions are added, then ventilation stablizes 20 minutes.

（3）The preparation of gel

In step（2）100g SiO are added in resulting slurries₂/ L sodium metasilicate working solution 1.5L and step（1）Prepare Directed agents 120g, the pH value of gel is 12, and 20 DEG C of controlling reaction temperature, uniform stirring 30 minutes staticizes 2 hours.

（4）Crystallization

By step（2）Resulting gel is poured in stainless steel cauldron, and crystallization is stirred 4 hours at 70 DEG C, is then heated up To 100 DEG C, stirring crystallization 8 hours, then filter, washing, dry NaY molecular sieve product NY-1, product property is shown in Table 1.

The preparation of NY-2

（1）The preparation of directed agents：Take 8 g sodium hydrate solids to be dissolved in 80g water, add the g (Al of sodium metaaluminate 2.5₂O₃ Content is 45wt%, Na₂O content is 41wt%).Then 40g waterglass (SiO are added₂Content is 28wt%, Na₂O content is 8 Wt%), in 18 DEG C of stirring 4 hours prepared directed agents of ageing after being well mixed.

（2）The preparation of amorphous silica-alumina predecessor

Solid sodium aluminate is configured to into concentration for 30gAl₂O₃/ L sodium aluminate working solutions, take containing SiO₂The silicic acid of 28wt% Sodium solution, then concentration is diluted to for 70g SiO₂/ L sodium metasilicate working solutions.Take 1L sodium aluminate working solutions to be placed in plastic cans, 0.4L sodium metasilicate working solutions are subsequently adding, 18 DEG C of controlling reaction temperature is passed through the CO that concentration is 50v%₂Gas, when pH value reaches To the logical CO of stopping when 10.2₂, 0.6L sodium metasilicate working solutions are added, then ventilation stablizes 20 minutes.

（3）The preparation of gel

In step（2）70g SiO are added in resulting slurries₂/ L sodium metasilicate working solution 1.5L and step（1）Prepare Directed agents 100g, the pH value of gel is 11.5, and 15 DEG C of controlling reaction temperature, uniform stirring 30 minutes staticizes 2.5 hours.

（4）Crystallization

By step（2）Resulting gel is poured in stainless steel cauldron, and crystallization is stirred 5 hours at 75 DEG C, is then heated up To 110 DEG C, stirring crystallization 7 hours, then filter, washing, dry NaY molecular sieve product NY-2, product property is shown in Table 1.

Embodiment 2

First alkali process are carried out to raw material small crystal grain NaY molecular sieve, be 1 mol/L by 1000 grams of NY-1 and 5L concentration NaOH solution beating is well mixed, and maintains stir process 2h under 80 DEG C of temperature conditionss, filters, is washed to during solution is close to Property；0.5mol/L aqueous ammonium nitrate solution of the filter cake with 10 liters is contacted, speed of agitator is 300rpm, the constant temperature stirring at 90 DEG C L hours, then filtering molecular is sieved, and stays sample, analyzes Na₂O content；Repeat aforesaid operations, the Na in molecular sieve₂O content 2.5wt% is reached, dried sample number into spectrum is obtained for NNY-1.

Embodiment 3

First alkali process are carried out to raw material small crystal grain NaY molecular sieve, be 0.8 mol/L by 1000 grams of NY-2 and 5L concentration KOH solution beating is well mixed, and maintains stir process 2h under 80 DEG C of temperature conditionss, filters, is washed to the close neutrality of solution； 0.5mol/L aqueous ammonium nitrate solution of the filter cake with 10 liters is contacted, speed of agitator is 300rpm, constant temperature stirring l is little at 95 DEG C When, then filtering molecular is sieved, and stays sample, analyzes Na₂O content；Repeat aforesaid operations, the Na in molecular sieve₂The content of O reaches To 2.5wt%, dried sample number into spectrum is obtained for NNY-2.

Embodiment 4

Take 100 grams of NNY-1 to be placed in heat-treatment furnace, control the heating rate of 500 DEG C/h, temperature is risen to into 600 DEG C, together When maintain system water vapor pressure be 0.15MPa, process 2 hours, cooling, take out sample；Sample is contained into NH with 500mL₄ ⁺And H⁺Concentration be respectively 0.6mol/L and 0.1mol/L mixed solution (ammonium chloride and hydrochloric acid) process, remove sample in non-bone Frame aluminium, dealuminzation condition is to process 2 hours at 80 DEG C, and washs filter cake with hot deionized water, to stop after the pH value of cleaning solution close 7 Only washing, filter cake 120 DEG C of dryings 5 hours in an oven, obtain modified small-grain Y -1.The physico-chemical property of Y-1 is shown in Table 1.

Embodiment 5

Take 100 grams of NNY-1 to be placed in heat-treatment furnace, control 400 DEG C/h of heating rate, temperature is risen to into 650 DEG C, The steam partial pressure 0.08MPa of system being maintained simultaneously, being processed 2 hours, sample is taken out in cooling；Sample is contained into NH with 400mL₄ ⁺And H⁺Concentration be respectively 0.8mol/L and 0.2mol/L mixed solution (ammonium nitrate and nitric acid) process, remove sample in non-bone Frame aluminium, dealuminzation condition is to process 3 hours at 70 DEG C, is filtered, and washs filter cake with hot deionized water, is connect with the pH value of cleaning solution Stop washing, filter cake 120 DEG C of dryings 5 hours in an oven after nearly 7, obtain modified small-grain Y -2.The physico-chemical property of Y-2 is shown in Table 1。

Embodiment 6

Take 100 grams of NNY-2 to be placed in hydro-thermal process stove, control 400 DEG C/h of heating rate, temperature is risen to into 700 DEG C, while the steam partial pressure 0.1MPa of the system of maintenance, is processed 2 hours, sample is taken out in cooling；Sample is contained into NH with 400mL₄ ⁺ And H⁺Concentration be respectively 1.0mol/L and 0.2mol/L mixed solution (ammonium chloride and hydrochloric acid) process, removing sample in Non-framework aluminum, dealuminzation condition is to process 3 hours to filter at 75 DEG C, and washs filter cake with hot deionized water, with the pH of cleaning solution Stop washing, filter cake 120 DEG C of dryings 6 hours in an oven after being worth close 7, obtain modified small-grain Y -3.The physico-chemical property of Y-3 It is shown in Table 1.

Embodiment 7

By 46 grams of Y-1 molecular sieves (butt 90wt%), 92 grams of amorphous silica-aluminas (pore volume 0.9ml/g, than

Surface area 350m²/ g, butt 70wt%), (butt 20wt%, nitric acid rubs 160 grams of adhesives with little porous aluminum oxide You are rolled into paste than 0.25) to be put into mixed grind in roller, adding water, extrusion, extrusion bar in 110 DEG C of dryings 4 hours, then In 550 DEG C of roastings 4 hours, carrier TCAT-1 is obtained, property is shown in Table 2.

Embodiment 8

By 40 grams of Y-1 molecular sieves (butt 90wt%), 100 grams of amorphous silica-aluminas (pore volume 0.9ml/g, than

Surface area 350m²/ g, butt 70wt%), (butt 20wt%, nitric acid rubs 160 grams of adhesives with little porous aluminum oxide You are rolled into paste than 0.25) to be put into mixed grind in roller, adding water, extrusion, extrusion bar in 110 DEG C of dryings 4 hours, then In 550 DEG C of roastings 4 hours, carrier TCAT-1 is obtained, property is shown in Table 2.

Embodiment 9

By 55 grams of Y-1 molecular sieves (butt 90wt%), 80 grams of amorphous silica-aluminas (pore volume 0.9ml/g, than

Surface area 350m²/ g, butt 70wt%), (butt 20wt%, nitric acid rubs 160 grams of adhesives with little porous aluminum oxide You are rolled into paste than 0.25) to be put into mixed grind in roller, adding water, extrusion, extrusion bar in 110 DEG C of dryings 4 hours, then In 550 DEG C of roastings 4 hours, carrier TCAT-2 is obtained.

The maceration extract room temperature immersion of carrier tungstenic and nickel 2 hours, 120 DEG C of dryings 4 hours, 500 DEG C of roastings 4 of temperature programming Hour, catalyst CAT-2 is obtained, carrier and corresponding catalyst property are shown in Table 2.

Comparative example 1

1st, fine grain NaY is prepared with reference to CN101722023A.

Feedstock property used is as follows in this comparative example：Low alkali sodium metaaluminate：Na₂O content 120g/L, Al₂O₃Content 40g/L；Waterglass：SiO₂Content 250g/L；Aluminum sulfate：Al₂O₃Content 90g/L.

(1) preparation of directed agents：The preparation of directed agents is with NY-1 in embodiment 1.

(2) preparation of gel：Temperature is 8 DEG C, under stirring condition, in the waterglass of 208mL 59.4mL sulphur is sequentially added Sour aluminium, the low sodium metaaluminate of 62.7mL and 42.2mL directed agents, then constant temperature constant speed stirring 1.5 hours, then by the conjunction for obtaining Into liquid static aging 8 hours at the temperature disclosed above, gel is obtained.

(3) crystallization：Under agitation, the gel in synthesis reactor is raised to into 50 DEG C in 20 minutes, constant temperature stirring crystallization 7 Hour；After low temperature crystallized end, the temperature in synthesis reactor is brought up to into 120 DEG C in 20 minutes, then constant temperature is stirred 6 hours. Jing is filtered, washs and is dried, and obtains product little crystal grain CNY-l.

2nd, ammonium exchange is carried out to raw material small crystal grain NaY molecular sieve, treatment conditions obtain dried sample with embodiment 2 Numbering is CNNY-1.

3rd, subsequent treatment is carried out to CNNY-1, processing mode and condition obtain Reference Product CY-1 with embodiment 4.CY-1 Physico-chemical property be shown in Table 1.

4th, by 40 grams of Y-1 molecular sieves (butt 90wt%), 100 grams of amorphous silica-aluminas (pore volume 1.0ml/g, than

Surface area 380m²/ g, butt 70wt%), (butt 20wt%, nitric acid rubs 160 grams of adhesives with little porous aluminum oxide You are rolled into paste than 0.25) to be put into mixed grind in roller, adding water, extrusion, extrusion bar in 110 DEG C of dryings 4 hours, then In 550 DEG C of roastings 4 hours, carrier TCCAT-1 is obtained.

The maceration extract room temperature immersion of carrier tungstenic and nickel 2 hours, 120 DEG C of dryings 4 hours, 500 DEG C of roastings 4 of temperature programming Hour, catalyst CCAT-1 is obtained, carrier and corresponding catalyst property are shown in Table 2.

Comparative example 2

1st, fine grain NaY is prepared with reference to CN1785807A.

The preparation of directed agents：The preparation of directed agents is with NY-1 in embodiment 1.

14.21g water is positioned in beaker, it is 60 DEG C to control fluid temperature in beaker, quick stirring is lower to be added simultaneously The A1 of 12.79g50wt%₂(SO₄)₃) solution and 31.91g waterglass.After stirring, above-mentioned directed agents 1.90g, gel are added PH value be 12.5, after stirring, in being loaded into stainless steel cauldron, at 60 DEG C crystallization 6 hours is stirred, then heat to 100 DEG C of static crystallizations 60 hours, then filter, washing, dry CNY-2 molecular sieves.

2nd, ammonium exchange is carried out to raw material small crystal grain NaY molecular sieve, treatment conditions obtain dried sample with embodiment 2 Numbering is CNNY-2.

3rd, subsequent treatment is carried out to CNNY-2, processing mode and condition obtain Reference Product CY-2 with embodiment 4.CY-2 Physico-chemical property be shown in Table 2.

4th, by 40 grams of Y-1 molecular sieves (butt 90wt%), 100 grams of amorphous silica-aluminas (pore volume 1.0ml/g, than

Surface area 380m²/ g, butt 70wt%), (butt 20wt%, nitric acid rubs 160 grams of adhesives with little porous aluminum oxide You are rolled into paste than 0.25) to be put into mixed grind in roller, adding water, extrusion, extrusion bar in 110 DEG C of dryings 4 hours, then In 550 DEG C of roastings 4 hours, carrier TCCAT-2 is obtained, property is shown in Table 2.

Comparative example 3

1st, prepared by fine grain NaY

（1）The preparation of directed agents：The preparation of directed agents is with NY-1 in embodiment 1.

（2）The preparation of amorphous silica-alumina predecessor.

Solid sodium aluminate is configured to into concentration for 40gAl₂O₃/ L sodium aluminate working solutions, take containing SiO₂The silicic acid of 28wt% Sodium solution, then concentration is diluted to for 100g SiO₂/ L sodium metasilicate working solutions.Take 1L sodium aluminate working solutions and be placed in plastic cans In, 0.6L sodium metasilicate working solutions are subsequently adding, 20 DEG C of controlling reaction temperature is passed through the CO that concentration is 50v%₂Gas, works as pH value Stop logical CO when reaching 10.0₂, then divulge information and stablize 20 minutes.

（3）The preparation of gel is with embodiment 1.

（4）Crystallization obtains products C NY-3 with embodiment 1, and product property is shown in Table 1.

2nd, ammonium exchange is carried out to raw material small crystal grain NaY molecular sieve, treatment conditions obtain dried sample with embodiment 2 Numbering is CNNY-3.

3rd, subsequent treatment is carried out to CNNY-3, processing mode and condition obtain Reference Product CY-3 with embodiment 4.CY-3 Physico-chemical property be shown in Table 2.

4th, by 55 grams of Y-1 molecular sieves (butt 90wt%), 80 grams of amorphous silica-aluminas (pore volume 0.9ml/g, specific surface areas 350m²/ g, butt 70wt%), (butt 20wt%, 0.25) mol ratio of nitric acid and little porous aluminum oxide to put for 160 grams of adhesives Enter mixed grind in roller, add water, be rolled into paste, extrusion, extrusion bar is then little in 550 DEG C of roastings 4 in 110 DEG C of dryings 4 hours When, carrier TCCAT-3 is obtained, property is shown in Table 2.

Comparative example 4

1st, the preparation of CNNY-4 is with comparative example 1.Then it is modified using the method for CN200910165116.X, it is specific as follows： 100 grams of CNNY-4 100mL deionized waters beating are taken, and is brought rapidly up under conditions of stirring to 95 DEG C, then with uniform Speed is added dropwise the aqueous solution configured by 25 grams of ammonium hexafluorosilicates and 150m1 deionized waters in 2 hours, adds rear slurry 95 2 hours of constant temperature under DEG C stirring condition, stand 10 minutes, through 3 washings, filter, be dried；Sample after above-mentioned drying is placed in In heat-treatment furnace, the heating rate of 500 DEG C/h is controlled, temperature is risen to into 600 DEG C, while the water vapor pressure of the system of maintenance is 0.15MPa, is processed 2 hours, and sample is taken out in cooling；Final sample contains Al with 400mL³⁺And H⁺Concentration be respectively 1.0mol/L With the non-framework aluminum in mixed solution (aluminum nitrate and nitric acid) the removing sample of 0.5mol/L, dealuminzation condition is to process 2 at 80 DEG C Hour, and filter cake is washed with hot deionized water, done for 120 DEG C in an oven with stopping washing, filter cake after the pH value of cleaning solution close 7 Dry 5 hours, obtain CY-4.The physico-chemical property of CY-4 is shown in Table 1.

2nd, by 40 grams of Y-1 molecular sieves (butt 90wt%), 100 grams of amorphous silica-aluminas (pore volume 1.0ml/g, than

Surface area 380m²/ g, butt 70wt%), (butt 20wt%, nitric acid rubs 160 grams of adhesives with little porous aluminum oxide You are rolled into paste than 0.25) to be put into mixed grind in roller, adding water, extrusion, extrusion bar in 110 DEG C of dryings 4 hours, then Carrier TCCAT-4 is obtained in 550 DEG C of roastings within 4 hours.

The maceration extract room temperature immersion of carrier tungstenic and nickel 2 hours, 120 DEG C of dryings 4 hours, 500 DEG C of roastings 4 of temperature programming Hour, catalyst CCAT-4 is obtained, carrier and corresponding catalyst property are shown in Table 2.

Comparative example 5

1st, fine grain NaY is prepared with reference to CN92105661.3

Feedstock property in this comparative example used by NaY is as follows：Low alkali sodium metaaluminate：Na₂O content 120g/L, Al₂O₃Content 40g/L；Waterglass：SiO₂Content 250g/L；Aluminum sulfate：Al₂O₃Content 90g/L.

(1) preparation of directed agents：The preparation of directed agents is with NY-1 in embodiment 1.

(2) preparation of gel：The low sodium metaaluminate of 60mL aluminum sulfate, 60mL is sequentially added in the waterglass of 220mL, Then constant temperature constant speed is stirred 0.5 hour, and silica-alumina gel is obtained.

(3) crystallization：Under agitation, the gel in synthesis reactor is raised to into 140 DEG C in 30 minutes, constant temperature stirring crystallization 2 hours；35mL directed agents, mixing and stirring are added then to continue crystallization 15 hours at 100 DEG C, Jing is filtered, washed and dry It is dry, products C NY-5 is obtained, product property is shown in Table 1.

2nd, ammonium exchange is carried out to raw material small crystal grain NaY molecular sieve CNY-3, treatment conditions obtain dried with embodiment 2 Sample number into spectrum is CNNY-5.

3rd, subsequent treatment is carried out to CNNY-5, processing mode and condition obtain Reference Product CY-5 with embodiment 4.CY-5 Physico-chemical property be shown in Table 1.

4th, by 40 grams of Y-1 molecular sieves (butt 90wt%), 100 grams of amorphous silica-aluminas (pore volume 1.0ml/g, than

Surface area 380m²/ g, butt 70wt%), (butt 20wt%, nitric acid rubs 160 grams of adhesives with little porous aluminum oxide You are rolled into paste than 0.25) to be put into mixed grind in roller, adding water, extrusion, extrusion bar in 110 DEG C of dryings 4 hours, then In 550 DEG C of roastings 4 hours, carrier TCCAT-5 is obtained.

Comparative example 6

1st, 100gNNY-1 is taken, the NNY-1 of the present invention is modified using the method for CN200910165116.X, it is concrete modified Method obtains Reference Product CY-6 with comparative example 4.The physico-chemical property of CY-6 is shown in Table 1.

2nd, by 55 grams of Y-1 molecular sieves (butt 90wt%), 80 grams of amorphous silica-aluminas (pore volume 0.9ml/g, specific surface areas 350m²/ g, butt 70wt%), (butt 20wt%, 0.25) mol ratio of nitric acid and little porous aluminum oxide to put for 160 grams of adhesives Enter mixed grind in roller, add water, be rolled into paste, extrusion, extrusion bar is then little in 550 DEG C of roastings 4 in 110 DEG C of dryings 4 hours When, obtain carrier TCCAT-6.

The maceration extract room temperature immersion of carrier tungstenic and nickel 2 hours, 120 DEG C of dryings 4 hours, 500 DEG C of roastings 4 of temperature programming Hour, catalyst CCAT-6 is obtained, carrier and corresponding catalyst property are shown in Table 2.

The property of the Y type molecular sieve of table 1

Production code member	NY-1	NY-2	Y-1	Y-2	Y-3	CY-1	CY-2	CY-3	CY-4	CY-5	CY-6
												Feed intake SiO2/Al2O3Mol ratio	9.1	10.1
SiO2/Al2O3Mol ratio	7.5	8.4	26	32	35	20	18	19	63	24	65
												Specific surface area, m2/g	916	898	952	931	927	880	861	875	921	711	935
Pore volume, mL/g	0.39	0.38	0.48	0.47	0.45	0.39	0.37	0.41	0.48	0.30	0.51
												Secondary pore（1.7-10nm）, %			50.1	56.4	61.2	40.1	27.5	35.2	42.1	25.2	44.0
External surface area, m2/g	191	182	264	244	233	170	169	190	189	145	209
												Lattice constant, nm	2.461	2.462	2.440	2.439	2.438	2.441	2.442	2.441	2.436	2.449	2.436
Relative crystallinity, %	101	110	108	104	105	86	81	82	116	78	117
												Average crystallite size, nm	380	430	380	380	430	470	450	400	400	450	400

The physico-chemical property of the carrier of table 2 and catalyst

Bearer number	TCAT-1	TCAT-2	TCAT-3	TCCAT-1	TCCAT-2	TCCAT-3	TCCAT-4	TCCAT-5	TCCAT-6
										Y molecular sieve, wt%	30	26	36	26	26	36	26	26	36
Amorphous silica-alumina, wt%	47	51	41	51	51	41	51	51	41
										Aluminum oxide, wt%	23	23	23	23	23	23	23	23	23
Specific surface area, m2/g	507	496	516	415	408	390	510	382	516
										Pore volume, ml/g	0.62	0.59	0.63	0.51	0.47	0.46	0.62	0.41	0.64
Pore size distribution（4-10nm）, %	52.0	58.6	63.8	41.2	29.3	36.9	44.3	27.2	44.1
										Catalyst is numbered			CAT-3	CCAT-1			CCAT-4		CCAT-6
Specific surface area, m2/g			409	301			411		415
										Pore volume, ml/g			0.55	0.40			0.54		0. 55
Pore size distribution（4-10nm）, %			53.1	36.2			40.1		43.2

The invention described above catalyst CAT-3 and comparative example catalyst CCAT-1 are carried out into active evaluation test.Test be Carry out on 200mL small hydrogenation devices, using one-stage serial>177 DEG C of fraction complete alternation technological processes, raw materials used oil nature It is shown in Table 3.Operating condition is as follows：Hydrogen dividing potential drop 14.7MPa, hydrogen to oil volume ratio 1500：1, air speed 1.5h^{- 1}, control cracking zone nitrogen content 5～10 g/g.Catalyst Activating Test the results are shown in Table 4.

The raw material oil nature of table 3

Feedstock oil	Iranian VGO
		Density (20 DEG C), g/cm3	0.9025
Boiling range, DEG C	308～560
		Condensation point, DEG C	33
Acid number, mgKOH/g	0.53
		Carbon residue, wt%	0.2
S, wt%	1.5
		N, wt%	0.11
C, wt%	84.93
		H, wt%	12.52
Aromatic hydrocarbons, wt%	39.2
		BMCI values	41.5
Refractive power/nD 70	1.48570

The catalyst activity evaluation result of table 4

Catalyst is numbered	CAT-3	CCAT-1	CCAT-4	CCAT-6
					Reaction temperature, DEG C	360	374	371	369
Heavy naphtha（65～177 DEG C）
					Yield, wt%	73.1	66.1	68.4	69.1
Aromatic hydrocarbons, wt%	4.3	6.2	5.8	5.2
					Virtue is latent, %	56.6	48.1	50.1	51.9
C5 +Liquid is received, wt%	92.33	89.44	90.01	90.98
					Chemical hydrogen consumption	2.40	3.30	3.24	3.26

Can be seen that by the evaluation result of the catalyst of table 4, the catalyst prepared by the present invention has on the basis of greater activity There is very high heavy naphtha yield, product property is good.

Claims (29)

1. a kind of carrier of hydrocracking catalyst, is made up of small crystal grain Y-shaped molecular sieve, amorphous silica-alumina and aluminum oxide, wherein institute The small crystal grain Y-shaped molecular sieve stated, its property is as follows：SiO₂/A1₂O₃10 less than 40, average grain diameter is mol ratio 200～700nm, relative crystallinity more than 100%, 2.430～2.450nm of lattice constant, specific surface area be 850～ 1000m²/ g, pore volume is 0.50～0.80mL/g, and the pore volume shared by the secondary pore of 1.7～10nm accounts for more than the 50% of total pore volume, Na₂O content≤0.15wt%.

2. according to the catalyst carrier described in claim 1, it is characterised in that：The SiO of described small crystal grain Y-shaped molecular sieve₂/ A1₂O₃Mol ratio is 15 ~ 38.

3. according to the catalyst carrier described in claim 1, it is characterised in that：In described small crystal grain Y-shaped molecular sieve, 1.7～ Pore volume shared by the secondary pore of 10nm accounts for the 50% ~ 65% of total pore volume.

4. according to the catalyst carrier described in claim 1, it is characterised in that：The structure cell of described small crystal grain Y-shaped molecular sieve is normal 2.435～2.445nm of number.

5. according to the catalyst carrier described in claim 1, it is characterised in that：The relative knot of described small crystal grain Y-shaped molecular sieve Brilliant degree is 100% ~ 120%.

6. according to the catalyst carrier described in claim 1, it is characterised in that SiO in described amorphous silica-alumina₂Weight content For 20%～60%, the pore volume of amorphous silica-alumina is 0.6～1.1 mL/g, and specific surface area is 300～500 m²/g。

7. according to the catalyst carrier described in claim 1, it is characterised in that the carrier of hydrocracking catalyst property is as follows： Specific surface area is 450～650 m²/ g, pore volume is 0.5～0.80 mL/g, the pore volume of 4 ~ 10nm of aperture account for total pore volume 45%～ 80%.

8. according to the catalyst carrier described in claim 1, it is characterised in that described carrier of hydrocracking catalyst, with carrier Weight on the basis of, its composition includes：The content of small crystal grain Y-shaped molecular sieve be 15wt%～50wt%, the content of amorphous silica-alumina For 20wt%～60wt%, the content of aluminum oxide is 10wt%～30wt%.

9. according to the catalyst carrier described in claim 1, it is characterised in that described carrier of hydrocracking catalyst, with carrier Weight on the basis of, its composition includes：The content of small crystal grain Y-shaped molecular sieve be 20wt%～40wt%, the content of amorphous silica-alumina For 30wt%～50wt%, the content of aluminum oxide is 15wt%～30wt%.

10. the preparation method of the arbitrary catalyst carrier of claim 1 ~ 9, including：By small crystal grain Y-shaped molecular sieve, amorphous Sial and mixed with adhesive made by aluminum oxide, extruded moulding, then drying and roasting, make carrier.

11. in accordance with the method for claim 10, it is characterised in that the preparation method of the small crystal grain Y-shaped molecular sieve, including：

（1）The preparation of small crystal grain NaY molecular sieve；

（2）By small crystal grain NaY molecular sieve with containing alkaline solution treatment；

（3）By step（2）The small crystal grain NaY molecular sieve for obtaining is prepared into Na₂Little crystal grain NH of O content≤2.5wt%₄NaY；

（4）To step（3）Obtain little crystal grain NH₄NaY molecular sieve carries out hydro-thermal process；

（5）By step（4）The molecular sieve for obtaining is with containing NH₄ ⁺And H⁺Mixed solution process, it is scrubbed and be dried, obtain little crystalline substance Grain Y type molecular sieve；

Wherein step（1）Described small crystal grain NaY molecular sieve, its property is as follows： SiO₂/Al₂O₃Mol ratio is not more than 6.0 and high In 9.0, average grain diameter is 200～700nm, the m of specific surface 800～1000²/ g, 0.30～0.45mL/g of pore volume, relative knot Brilliant degree is 90%～130%, and cell parameter is 2.460～2.470nm, the relative crystallinity Jing after roasting in 650 DEG C of air 3 hours For more than 90%, relative crystallinity is more than 90% Jing after 700 DEG C of water vapour hydro-thermal process 2 hours.

12. in accordance with the method for claim 11, it is characterised in that：The SiO of described small crystal grain NaY molecular sieve₂/Al₂O₃Rub You are than being 6.5～9.0.

13. in accordance with the method for claim 11, it is characterised in that：The SiO of described small crystal grain NaY molecular sieve₂/Al₂O₃Rub You are than being 7.0～8.0.

14. in accordance with the method for claim 11, it is characterised in that：In described 650 DEG C of air of small crystal grain NaY molecular sieve Jing Relative crystallinity is 90%～110% after roasting 3 hours, and relative crystallinity is Jing after 700 DEG C of water vapour hydro-thermal process 2 hours 90%～110%.

15. in accordance with the method for claim 11, it is characterised in that step（1）The preparation of described small crystal grain NaY molecular sieve Method, including：

I, preparation directed agents：Silicon source, silicon source, alkali source and water are fed intake according to following proportioning：(6～30) Na₂O：Al₂O₃：(6～ 30)SiO₂：(100～460) H₂O, after stirring, mixture is stirred to be aged to be obtained for 0.5～24 hour at 0～20 DEG C and is led To agent；

II, using preparing amorphous silicon alumnium using carbonization predecessor, on the basis of the weight of the butt of amorphous silica-alumina predecessor, The content that silicon is counted with silica as 40wt%～75wt%；Its preparation process includes：

A, respectively preparation sodium aluminate solution and sodium silicate solution；

The part sodium silicate solution for adding step a to prepare in b, the sodium aluminate solution prepared to step a, then passes to CO₂Gas, Controlling reaction temperature is 10 ~ 40 DEG C, and the pH value for controlling cemented into bundles is 8 ~ 11；Wherein as the CO being passed through₂Gas flow is accounted for and is always passed through Amount 60% ~ 100% when, add remainder sodium silicate solution, remainder sodium silicate solution is with silica wherein in step b Meter accounts for step b and adds 5wt% ~ 85wt% of the sodium silicate solution total amount in terms of silica；

C, at the control temperature and pH value of step b, said mixture ventilation stablize 10 ~ 30 minutes；

III, prepare silica-alumina gel：By (0.5～6) Na₂O：Al₂O₃：(8～15) SiO₂：(100～460) H₂O's always feeds intake mole Than adding in the amorphous silica-alumina predecessor obtained by step II water, silicon source, guiding under conditions of 0～40 DEG C of quick stirring Agent and alkali source, and control ph is 9.5 ~ 12.0, uniform stirring obtains silica-alumina gel；Wherein directed agents addition accounts for sial and coagulates The 1%～20% of glue weight,

The step dynamic crystallizations of reactant mixture Jing two obtained by IV, step III, then Jing filtrations, washing, are dried, and obtain little crystal grain NaY molecular sieve.

16. in accordance with the method for claim 15, it is characterised in that in step II, amorphous silica-alumina predecessor, with amorphous On the basis of the weight of the butt of sial predecessor, the content that silicon is counted with silica is as 55 wt%～70wt%.

17. in accordance with the method for claim 15, it is characterised in that：Step b controlling reaction temperature is 15～35 DEG C.

18. in accordance with the method for claim 15, it is characterised in that：In step b, as the CO being passed through₂Gas flow accounts for total intake 80% ~ 100% when, add remainder sodium silicate solution.

19. in accordance with the method for claim 15, it is characterised in that：Remainder sodium silicate solution is with titanium dioxide in step b Silicon meter accounts for step b and adds 30wt% ~ 70wt% of the sodium silicate solution total amount in terms of silica.

20. in accordance with the method for claim 15, it is characterised in that in step I and III, and silicon source, alkali source are respectively selected from silicic acid Sodium and NaOH, in step I, silicon source is selected from sodium metaaluminate.

21. in accordance with the method for claim 15, it is characterised in that in step III, 10 ~ 30 DEG C of controlling reaction temperature, pH value 10～11.

22. in accordance with the method for claim 15, it is characterised in that step IV adopts two step dynamic crystallizations, wherein the first stepping The condition of Mobile state crystallization is as follows：At 50～90 DEG C, crystallization time is 0.5～18 hour to temperature control；Second step enters Mobile state The condition of crystallization is as follows：At 80～140 DEG C, crystallization time is 3～10 hours to temperature control.

23. in accordance with the method for claim 15, it is characterised in that step IV adopts two step dynamic crystallizations, wherein the first stepping The condition of Mobile state crystallization is as follows：At 60～80 DEG C, crystallization time is 1～10 hour to temperature control；It is brilliant that second step enters Mobile state The condition of change is as follows：At 80～120 DEG C, crystallization time is 5～10 hours to temperature control.

24. in accordance with the method for claim 11, it is characterised in that step（2）In, by small crystal grain NaY molecular sieve and the water of alkali Solution beating is well mixed, and maintains 1～4h of stir process under 60～120 DEG C of temperature conditionss；Alkali wherein used be NaOH, The mixture of KOH or NaOH and KOH；The concentration of the aqueous solution of alkali is 0.1～3 mol/L, and the concentration of molecular sieve is in slurries 0.05～1.0g/mL.

25. in accordance with the method for claim 11, it is characterised in that step（4）In, the condition of described hydro-thermal process is as follows： At 500～750 DEG C, pressure is 0.01～0.50MPa for treatment temperature control, and process time is 1.0～4.0 hours.

26. in accordance with the method for claim 11, it is characterised in that step（4）In, the condition of described hydro-thermal process is as follows： At 600～700 DEG C, pressure is 0.05～0.30MPa for treatment temperature control, and process time is 1.0～4.0 hours.

27. in accordance with the method for claim 11, it is characterised in that step（5）In, by the molecular sieve after hydro-thermal process and acid With containing NH₄ ⁺Salt composition mixed solution contact, acid therein is one or more in hydrochloric acid, carbonic acid, nitric acid, sulfuric acid, is contained NH₄ ⁺Salt be containing above acid group ammonium salt in one or more；H in mixed solution⁺Concentration be 0.05～0.6mol/L, NH₄ ⁺Concentration be 0.5～3.0mol/L, exchange temperature be 70～120 DEG C, exchange slurries in molecular sieve concentration be 0.1～ 0.5g/mL, swap time is 0.5～3.0 hour, and exchange step repeats 1～4 time.

28. in accordance with the method for claim 11, it is characterised in that：Step（3）The method exchanged using ammonium salt, process is such as Under：With NaY molecular sieve as raw material, exchanged 0.5～3.0 hour at 70～120 DEG C with the aqueous solution of soluble ammonium salt, molecular sieve Concentration in slurries are exchanged is 0.05～0.50g/mL, and repeated exchanged l～5 time filter off mother liquor, and washing is dried；Ammonium salt is chlorine Change one or more in ammonium, ammonium carbonate, ammonium nitrate, ammonium sulfate, ammonium acetate, ammonium oxalate, ammonium citrate, the concentration of ammonium salt solution For 0.5～5.0mol/L.

29. in accordance with the method for claim 10, it is characterised in that：The drying of carrier and roasting condition are as follows：Jing 80 ~ 150 DEG C drying 3 ~ 10 hours, in 500 ~ 600 DEG C of roastings 3 ~ 6 hours.